通过改变 L-Dap/Aib 螺旋肽中二茂铁-二茂铁的互易位置来调节二茂铁-二茂铁之间的相互作用

IF 3.1 4区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR
Annalisa Bisello, Barbara Biondi, Roberta Cardena, Renato Schiesari, M. Crisma, F. Formaggio, S. Santi
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引用次数: 0

摘要

在这项工作中,我们开发了两种新的多官能团杂交系统,其中肽支架上的 Fc 氧化还原 "天线 "可以调节其电子特性。具体来说,我们合成了两种螺旋六肽,其中含有四个 Aib(α-氨基异丁酸)和两个 L-Dap(2,3-二氨基丙酸)残基。然后用 Fc 分子对 L-Dap 侧链进行功能化。通过 X 射线衍射、二维核磁共振、CD 和红外光谱研究了两种 310 螺旋肽的结构,即 Z-Aib-L-Dap(Fc)-Aib-Aib-L-Dap(Fc)-Aib-NH-iPr 和 Z-Aib-L-Dap(Fc)-Aib-L-Dap(Fc)-Aib-Aib-NH-iPr。由于存在螺旋构象,Z-Aib-L-Dap(Fc)-Aib-Aib-L-Dap(Fc)-Aib-NH-iPr 中的 Fc 基团位于螺旋的同一个面上,而 Z-Aib-L-Dap(Fc)-Aib-L-Dap(Fc)-Aib-Aib-NH-iPr 中的 Fc 基团则位于相反的面上。令人惊讶的是,Z-Aib-L-Dap(Fc)-Aib-L-Dap(Fc)-Aib-Aib-NH-iPr 通过 DPV 发现了两条带,表明 Fc 基团之间存在静电相互作用,尽管它们的相互距离比 Z-Aib-L-Dap(Fc)-Aib-Aib-L-Dap(Fc)-Aib-NH-iPr 中的距离更长。在不同浓度下进行的 CD 实验表明,即使在高稀释度下,Z-Aib-L-Dap(Fc)-Aib-L-Dap(Fc)-Aib-Aib-NH-iPr 也会发生聚集,这表明 Fc-Fc 静电作用可能具有分子间性质。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Modulation of Ferrocene–Ferrocene Interactions by Varying Their Reciprocal Positions in L-Dap/Aib Helical Peptides
In this work, we developed two new polyfunctional hybrid systems in which the presence of Fc redox “antennas” on peptide scaffolds allows for a modulation of their electronic properties. Specifically, we synthesized two helical hexapeptides containing four Aib (α-amionoisobutyric acid) and two L-Dap (2,3-diamino propionic acid) residues. L-Dap side chains were then functionalized with Fc moieties. The structures of the two 310 helical peptides, namely Z-Aib-L-Dap(Fc)-Aib-Aib-L-Dap(Fc)-Aib-NH-iPr and Z-Aib-L-Dap(Fc)-Aib-L-Dap(Fc)-Aib-Aib-NH-iPr, were investigated by X-ray diffraction, 2D-NMR, CD and IR spectroscopies. Due to the helical conformation, in Z-Aib-L-Dap(Fc)-Aib-Aib-L-Dap(Fc)-Aib-NH-iPr, the Fc groups are located on the same face of the helix, but in Z-Aib-L-Dap(Fc)-Aib-L-Dap(Fc)-Aib-Aib-NH-iPr, they are located on opposite faces. Surprisingly, two bands were found through DPV for Z-Aib-L-Dap(Fc)-Aib-L-Dap(Fc)-Aib-Aib-NH-iPr, indicating an electrostatic interaction between the Fc groups despite their longer reciprocal distance with respect to that in Z-Aib-L-Dap(Fc)-Aib-Aib-L-Dap(Fc)-Aib-NH-iPr. CD experiments at different concentrations evidenced aggregation for Z-Aib-L-Dap(Fc)-Aib-L-Dap(Fc)-Aib-Aib-NH-iPr, even at high dilutions, thus suggesting that the Fc-Fc electrostatic interaction could be of an intermolecular nature.
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来源期刊
Inorganics
Inorganics Chemistry-Inorganic Chemistry
CiteScore
2.80
自引率
10.30%
发文量
193
审稿时长
6 weeks
期刊介绍: Inorganics is an open access journal that covers all aspects of inorganic chemistry research. Topics include but are not limited to: synthesis and characterization of inorganic compounds, complexes and materials structure and bonding in inorganic molecular and solid state compounds spectroscopic, magnetic, physical and chemical properties of inorganic compounds chemical reactivity, physical properties and applications of inorganic compounds and materials mechanisms of inorganic reactions organometallic compounds inorganic cluster chemistry heterogenous and homogeneous catalytic reactions promoted by inorganic compounds thermodynamics and kinetics of significant new and known inorganic compounds supramolecular systems and coordination polymers bio-inorganic chemistry and applications of inorganic compounds in biological systems and medicine environmental and sustainable energy applications of inorganic compounds and materials MD
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